Gas-phase reaction of two unsaturated ketones with atomic Cl and O-3: kinetics and products
Gas-phase reaction of two unsaturated ketones with atomic Cl and O-3: kinetics and products
复制标题
两种不饱和酮与原子 Cl 和 O-3 的气相反应：动力学和产物
DOI：
10.1039/c4cp05461j
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发表时间：
2015
影响因子：
3.3
通讯作者：
Ge Maofa
中科院分区：
文献类型：
--
作者：
Wang Jing;Zhou Li;Wang Weigang;Ge Maofa
在293 ± 1 K和大气压下，在100 L聚四氟乙烯室中测定了Cl原子和O3分子与3-甲基-3-丁烯-2-酮（MBO 332）和3-甲基-3-戊烯-2-酮（MPO 332）反应的速率常数和产物。对于MBO 332和MPO 332，使用相对速率法，用原子Cl测量的速率常数分别为（2.38 ± 0.26）× 10−10和（3.00 ± 0.34）× 10−10 cm 3 molecule−1 s−1。使用绝对速率法，测得O3的速率常数为（1.18 ± 0.21）× 10−17和（4.07 ± 0.45）× 10−17 cm 3 molecule−1 s−1。用质子转移反应质谱（PTR-MS）研究了这些反应的产物。结果表明，在原子氯反应中观察到的主要产物是甲醛和氯丙酮MBO 332，和乙醛和CH 3C（O）C（O）Cl的MPO 332。对于O3反应，MBO 332的主要产物是丁二酮和甲醛，而MPO 332的主要产物是丁二酮和乙醛。提出并讨论了可能的反应机理，并讨论了这些反应的大气影响。
The rate constants and products for the reactions of atomic Cl and O3 molecule with 3-methyl-3-buten-2-one (MBO332) and 3-methyl-3-penten-2-one (MPO332) were determined in a 100 L Teflon chamber at 293 ± 1 K and atmospheric pressure. For MBO332 and MPO332, the rate constants measured with atomic Cl were (2.38 ± 0.26) × 10−10 and (3.00 ± 0.34) × 10−10 cm3 molecule−1 s−1 using the relative rate method. Using the absolute rate method, the rate constants with O3 measured were (1.18 ± 0.21) × 10−17 and (4.07 ± 0.45) × 10−17 cm3 molecule−1 s−1. The products of these reactions were investigated by the proton-transfer-reaction mass spectrum (PTR-MS). The results indicated that the major products observed in the atomic Cl reaction were formaldehyde together with chloroacetone for MBO332, and acetaldehyde and CH3C(O)C(O)Cl for MPO332. For O3 reactions, butanedione and formaldehyde were the main products of MBO332, while butanedione and acetaldehyde were the main products of MPO332. Possible reaction mechanisms were proposed and discussed and the atmospheric implications of these reactions were also discussed.